Diffractive optical element, optical apparatus using the same, and method for manufacturing diffractive optical element

ABSTRACT

A diffractive optical element includes a substrate, a first resin layer formed on the substrate and having a diffraction grating shape including a plurality of wall surfaces and a plurality of slopes, a second resin layer formed in close contact with the first resin layer, a high refractive-index portion formed on the plurality of wall surfaces of the first resin layer and having a higher refractive index than the first and the second resin layers, and a close contact portion discontinuous with the high refractive-index portion, wherein the close contact portion is formed on the plurality of slopes of the first resin layer, and wherein a thickness of the close contact portion is smaller than a height of the plurality of wall surfaces.

BACKGROUND OF THE INVENTION Field of the Invention

The present disclosure relates to a diffractive optical element used foroptical apparatuses, such as still and video cameras. More particularly,the present disclosure relates to a diffractive optical element usingtwo different types of resin having different optical characteristics,an optical apparatus using the same, and a method for manufacturing thediffractive optical element.

Description of the Related Art

A diffractive optical element using two different types of opticalmembers having different optical characteristics is known as adiffractive optical element used as a lens. This diffractive opticalelement utilizes the characteristics in which chromatic aberration iscompletely conversely generated between a diffractive optical system anda refractive optical system to restrict chromatic aberration as a lens,and remarkably reduces the size and weight of the entire lens. With therecent improvement in image quality of optical apparatuses, such asstill and video cameras, higher levels of optical performance of lensesare required.

For example, a brochure of international publication of WO2011-099550discusses a technique for providing a high refractive-index member(waveguide) having a higher refractive index than two optical elementson wall surfaces (vertical faces) of a diffractive optical element inorder to reduce the generation of flare light resulting from thediffraction grating shape.

However, in a conventional diffractive optical element, the generationof flare light was unable to be reduced after being left in ahigh-temperature environment for a long period of time.

SUMMARY OF THE INVENTION

According to an aspect of the present disclosure, a diffractive opticalelement includes a substrate, a first resin layer formed on thesubstrate and having a diffraction grating shape including a pluralityof wall surfaces and a plurality of slopes, a second resin layer formedin close contact with the first resin layer, a high refractive-indexportion formed on the plurality of wall surfaces of the first resinlayer and having a higher refractive index than the first and the secondresin layers, and a close contact portion discontinuous with the highrefractive-index portion, wherein the close contact portion is formed onthe plurality of slopes of the first resin layer, and wherein athickness of the close contact portion is smaller than a height of theplurality of wall surfaces.

Further features of the present disclosure will become apparent from thefollowing description of exemplary embodiments with reference to theattached drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 schematically illustrates a diffractive optical element accordingto an exemplary embodiment of the present disclosure.

FIG. 2 schematically illustrates the diffractive optical elementaccording to an exemplary embodiment of the present disclosure.

FIG. 3 schematically illustrates the diffractive optical elementaccording to an exemplary embodiment of the present disclosure.

FIGS. 4A, 4B, 4C, 4D, and 4E schematically illustrate a method formanufacturing the diffractive optical element according to an exemplaryembodiment of the present disclosure.

FIG. 5 schematically illustrates an optical apparatus according to anexemplary embodiment of the present disclosure.

FIG. 6 schematically illustrates the diffractive optical elementaccording to an exemplary embodiment of the present disclosure.

FIG. 7 schematically illustrates the diffractive optical elementaccording to an exemplary embodiment of the present disclosure.

FIG. 8 schematically illustrates a diffractive optical element accordingto a conventional technique.

DESCRIPTION OF THE EMBODIMENTS

<Diffractive Optical Element>

FIG. 1 is a top view and a side view illustrating a diffractive opticalelement according to an exemplary embodiment of the present disclosure.FIG. 2 is a partial enlarged view illustrating the diffractive opticalelement illustrated in FIG. 1 .

A diffractive optical element 100 is composed of a first resin layer 1having a diffraction grating shape and a second resin layer 2 stacked inthis order in close contact on a first substrate 5. The diffractiongrating shape is composed of a plurality of wall surfaces 1A and aplurality of slopes 1B. A high refractive-index portion 3 is formed onthe wall surface 1A. The high refractive-index portion 3 has a higherrefractive index than the first resin layer 1 and the second resin layer2.

<Substrate>

The first substrate 5 is a transparent substrate. For example, S-LAH55(Ohara Inc.) as high-refractive-index low-dispersion glass of thelanthanum system and S-FPL51 (Ohara Inc.) as super-low-dispersion glasscan be used. Although, in FIG. 1 , the first substrate 5 is a meniscuslens, a planar lens can also be used. In addition, a second substratemay be disposed on the second resin layer 2. Like the first substrate,for example, a transparent substrate can be used as the secondsubstrate.

<Resin Layers>

The first resin layer 1 and the second resin layer 2 are made of, forexample, a transparent and colorless resin for optical use. Therefractive index and the Abbe number are designed to be able to achievethe desired optical characteristics of the diffractive optical element100. To achieve a high diffractive efficiency in a wide wavelength band,it is desirable that the first resin layer 1 provides a low refractiveindex and high dispersion, and the second resin layer 2 provides a highrefractive index and low dispersion. Low and high refractive indicesmean a relative relation between the refractive indices of the firstresin layer 1 and the second resin layer 2. Likewise, high and lowdispersions mean a relative relation between the dispersioncharacteristics (Abbe number νd) of the first resin layer 1 and thesecond resin layer 2. This means that, when the first resin layer 1 hasa refractive index nd1 and an Abbe number ν1, and the second resin layer2 has a refractive index nd2 and an Abbe number ν2, relations nd1<nd2and ν1<ν2 are satisfied.

In order to obtain a high diffractive efficiency of 99% or more in theentire visible region, it is desirable that the first resin layer 1 ismade of a resin having the linear dispersion characteristics with asmall partial dispersion ratio θgF. In order to obtain the lineardispersion characteristics, the resin may contain inorganic oxide fineparticles (with an average particle diameter of about 5 to 20 nm).Usable resins include curable resins such as a thermosetting resin andan ultraviolet curable resin. More specifically, an epoxy resin and anacrylic resin are desirable. Examples of usable inorganic oxide fineparticles include Sn-doped indium oxide (ITO) and Sb-doped indium oxide(ATO).

The first resin layer 1 has a diffraction grating shape composed of aplurality of wall surfaces 1A and a plurality of slopes 1B. In planarview from the stacking direction, this diffraction grating shape forms aconcentric relief pattern composed of a plurality of circles centeringon an optical axis O. The grating pitch of the relief pattern is largenear the center of the diffractive optical element 100 and decreaseswith increasing distance toward the outermost edge to generate theconverging effect and diverging effect of light. The length of eachslope of the diffraction grating is, for example, 100 μm or more and 5mm or less. The height of each wall surface of the diffraction gratingis, for example, 5 μm or more and 40 μm or less.

Like the first resin layer 1, resins usable for the second resin layer 2include curable resins such as a thermosetting resin and an ultravioletcurable resin. More specifically, an epoxy resin and an acrylic resinare desirable. Examples of usable inorganic oxide fine particles includezirconium dioxide and titanium oxide.

<High Refractive-Index Portion>

A high refractive-index portion 3 is formed on the wall surface 1A ofthe first resin layer 1 and is made of a material having a higherrefractive index than the first resin layer 1 and the second resin layer2. More specifically, glass and other inorganic materials are can be.Thus, the high refractive-index portion 3 is made of a material having asmaller linear expansion coefficient than the first resin layer 1 andthe second resin layer 2. More specifically, one or a plurality ofmixtures out of A₂O₃, HfO₂, ZrO₂, La₂O₃, and TiO₂ are can be used. Fromthe viewpoint of cost reduction, it is desirable to use Al₂O₃, La-dopedAl₂O₃, or Ti-doped Al₂O₃. Disposing the high refractive-index portion 3on the wall surface 1A makes it possible to reduce flare light(particularly grating flare) generated from the wall surface 1A.

It is desirable that the length (parallel to the wall surface 1A) of thehigh refractive-index portion 3 is the same as the height of the wallsurface 1A, for example, 5 μm or more and 40 μm or less. If the lengthof the high refractive-index portion 3 is smaller than the height of thewall surface 1A, the diffractive efficiency of the diffractive opticalelement 100 may become insufficient. The length of the highrefractive-index portion 3 may be larger than the height of the wallsurface 1A, and a part of the high refractive-index portion 3 may beformed on a slope 1B.

The thickness (length in the direction perpendicular to the wall surface1A) of the high refractive-index portion 3 is, for example, 10 nm ormore and 1.0 μm or less. If the thickness is within this range, flarelight generated from the wall surface 1A can be efficiently restricted.

<Close Contact Portion>

A close contact portion 4 is formed on the slope 1B of the first resinlayer 1. The thickness of the close contact portion 4 (length in thedirection perpendicular to the slope 1B) is smaller than the height ofthe wall surface 1A. If the thickness of the close contact portion 4formed on the slope 1B is smaller than the height of the wall surface1A, peeling between the resin layers is unlikely to occur on the slope1B. This enables offering a diffractive optical element that is unlikelyto be affected by dispersion flare. The reason for this phenomenon is asfollows. The close contact portion 4 formed on the slope 1B makes thecompressive stress concentrated on the high refractive-index portion 3disperse to also the close contact portion 4, and what is called theanchor effect occurs between the resin layers on the slope 1B. Even ifpeeling occurs at an end of the wall surface 1A by the compressivestress applied to the end of the high refractive-index portion 3, theanchor effect prevents peeling from progressing toward the slope 1B.

In this case, the thickness of the close contact portion 4 is preferably1/400 or more and 1/50 or less times the height of the wall surface 1A.More preferably, the thickness is 10 nm or more and 200 nm or less. Ifthe thickness of the close contact portion 4 is less than 10 nm, theconcavo-convex shape is too shallow and possibly prevent the anchoreffect from occurring. In addition, if stress is applied to the closecontact portion 4, the close contact portion 4 may crack since it isthin. On the other hand, if the thickness of the close contact portion 4exceeds 200 nm, dispersion flare may occur from the close contactportion 4 because of Rayleigh dispersion.

The close contact portion 4 is formed discontinuously with the highrefractive-index portion 3 as a different member from the highrefractive-index portion 3. If the close contact portion 4 is formedcontinuously with the high refractive-index portion 3, the compressivestress concentrates on the close contact portion 4, not on both ends ofthe high refractive-index portion 3, increasing the possibility of thecracking of the close contact portion 4. If the close contact portion 4cracks, it become impossible to prevent flare light resulting in adegraded diffractive efficiency.

It is desirable that the covering area of the close contact portion 4 tothe slope 1B is 5 or more and 99 or less area portions with respect to100 area portions of the slope 1B. If the covering area is within thisrange, the compressive stress occurring in the high refractive-indexportion 3 provided on the wall surface 1A and the compressive stressoccurring on the close contact portion 4 can be mutually moved anddispersed. This enables increasing the probability of restrictingpeeling occurring in the interface between the first resin layer 1 andthe second resin layer 2. On the other hand, if the covering area isless than 5 area portions, the compressive stress concentrates on thehigh refractive-index portion 3, and peeling may progress to the slope1B.

It is desirable that the close contact portion 4 is disposed in a regionsatisfying a condition 0.1R≤|r|≤R, where R denotes the radius of thediffractive optical element 100 and r denotes the distance from a centerO (corresponding to optical axis O) of the diffractive optical element100 in the outer edge direction (radial direction) when the diffractiveoptical element 100 is viewed (planar view) from the stacking direction(refer to FIG. 3 ). This is because, if the close contact portion 4 isnot disposed within the range from the center of the diffractive opticalelement 100 to 0.1R, the transmitted wave front of the diffractiveoptical element 100 can be made preferable. In a region near theoutermost edge of the diffractive optical element 100, the small pitchinterval between gratings may cause the interference and synergisticeffect between the stresses of adjoining high refractive-index portions3. In a range from the center of the diffractive optical element 100 toless than 0.1R, the pitch interval between gratings is large enough.Therefore, in a range from the center of the diffractive optical element100 to less than 0.1R, the probability that peeling occurs is low evenif the close contact portion 4 is not provided.

It is desirable that the thickness of the close contact portion 4increases with increasing distance from the center toward the outer edgeof the diffractive optical element 100. It is also desirable that thecovering area of the close contact portion 4 to the slope 1B increaseswith increasing distance from the center toward the outer edge of thediffractive optical element 100. The synergistic effect of the stressoccurring from adjoining high refractive-index portions 3 increases withincreasing distance from the center toward the outer edge (having asmaller grating pitch) of the diffractive optical element 100.Therefore, increasing the thickness and the covering area of the closecontact portion 4 with increasing distance from the center toward theouter edge of the diffractive optical element 100 enhances the anchoreffect, providing a structure more resistant to peeling.

It is desirable that the close contact portion 4 forms sea-islandstructures as illustrated in FIG. 2 on the slope 1B. This is because,even with the same covering area, forming sea-island structures expandsconcavo-convex regions and makes it possible to enhance the anchoreffect compared to the uniform covering state. Referring to FIG. 2 ,sea-island structures are formed with the close contact portion 4 asislands and the slope 1B as the sea.

The material of the close contact portion 4 is not particularly limitedas long as the material is transparent and provides a sufficient closecontact between the first resin layer 1 and the second resin layer 2.However, it is desirable that the material has a close refractive indexto the first resin layer 1 and the second resin layer 2 in order toobtain a high diffractive efficiency.

It is desirable that the material of the close contact portion 4 is thesame as the material of the high refractive-index portion 3. This makesit easier to simultaneously form the close contact portion 4 and thehigh refractive-index portion 3, thus reducing the manufacturing cost.

It is desirable that the linear expansion coefficient of the closecontact portion 4 at 0 to 40° C. is 1/10 times the linear expansioncoefficient of the first resin layer 1 and the second resin layer 2 at 0to 40° C. This is because, if the linear expansion coefficient is 1/10or less times, i.e., an excessively large difference between the linearexpansion coefficients of the close contact portion 4 and the resinlayers (first resin layer 1 and second resin layer 2) may possibly causepeeling in the interface between the close contact portion 4 and theresin layers.

In addition, the higher the material affinity between the close contactportion 4 and the resin layers (first resin layer 1 and second resinlayer 2), the more intensively the anchor effect occurs. For example, ifa hydroxyl group exists on the surface of the close contact portion 4, ahydroxyl group strongly bonded by the hydrogen bond also exists in thefirst resin layer 1 and the second resin layer 2. Accordingly, it can beexpected that the anchor effect is enhanced.

Although the close contact portion 4 is cylindrically shaped asillustrated in FIG. 2 , the shape of the close contact portion 4 is notbe limited thereto and may be a polygonal column, polygonal pyramid, orcone.

<Diffractive Optical Element by Conventional Technique>

FIG. 8 schematically illustrates a diffractive optical element by theconventional technique. A diffractive optical element 900 includes anoptical element 901 having a diffraction grating shape composed of aplurality of wall surfaces 901A and a plurality of slopes 901B, a highrefractive-index member 902 disposed on the wall surfaces 901A, and anoptical element 903. The high refractive-index member 902 is designed tohave a higher refractive index than the optical elements 901 and 903.Thus, for example, the high refractive-index member 902 is made of aninorganic material, and the optical elements 901 and 903 are made of anorganic material. Since the linear expansion coefficient of organicmaterials is generally larger than the linear expansion coefficient ofinorganic materials, the linear expansion coefficient of the opticalelements 901 and 903 is larger than the linear expansion coefficient ofthe high refractive-index member 902. Accordingly, under ahigh-temperature environment, the optical elements 901 and 903 expandmore than the high refractive-index member 902, and the compressivestress is applied to both ends of the high refractive-index member 902(portions enclosed in dotted lines illustrated in FIG. 8 ) from theoptical elements 901 and 903. As a result, starting from both ends ofthe high refractive-index member 902, peeling occurs over the entireinterface between the optical elements 901 and 903 in the vicinity ofthe slopes 901B. Therefore, under a high-temperature environment, thegeneration of flare light was unable to be reduced even if the highrefractive-index member 902 is used.

<Method of Manufacturing Diffractive Optical Element>

A method for manufacturing the diffractive optical element according tothe present disclosure will be described below.

FIGS. 4A to 4E schematically illustrate a method for manufacturing thediffractive optical element according to an exemplary embodiment of thepresent disclosure.

As illustrated in FIG. 4A, a first resin 11 as a precursor of the firstresin layer is formed between a first substrate 5 and a mold 10. Themold 10 has an inverted shape of a desired diffraction grating shape andis made of stainless steel (such as SUS material and STAVAX from BohlerUddeholm AG (BUAG)) or NiP. The first resin 11 is a resin containing acurable resin. The following describes an example where an ultravioletcurable resin is used.

Then, as illustrated in FIG. 4B, the first resin 11 is press-transferredonto the first substrate 5 by using a pressing jig 15 as a transparentsubstrate made of the same material as the first substrate 5.Subsequently, the first resin 11 is irradiated with ultravioletradiation from an ultraviolet light source 9 through the pressing jig 15and the first substrate 5. When the first resin 11 is irradiated withultraviolet radiation to be cured and then the mold 10 is released, afirst resin layer 1 having a diffraction grating shape is formed (thisintermediate member is referred to as a lens A).

Subsequently, as illustrated in FIG. 4C, a high refractive-index portion3 is formed on the wall surfaces of the diffraction grating of the lensA by using a vapor deposition method. When the high refractive-indexportion 3 is formed using the mask 13, the lens A is tilted by a desiredangle with respect to a vapor deposition source 14 and then rotated at adesired speed centering on the optical axis. Then, the highrefractive-index portion 3 having a uniform thickness in thecircumferential direction is formed.

The close contact portion 4 is formed on the slope of the diffractiongrating of the lens A by using the vapor deposition method. Unlike thetime of forming the high refractive-index portion 3, the vapordeposition source 14 is disposed perpendicularly to the lens A, and theclose contact portion 4 is formed (this intermediate member is referredto as a lens B). In this case, in order not to form the close contactportion 4 on the wall surfaces, a mask is used tailored to the annularinterval of the diffraction grating shape. When the same the material isused for the close contact portion 4 and the high refractive-indexportion 3, the close contact portion 4 and the high refractive-indexportion 3 can be continuously formed. In addition, sea-island structuresof the close contact portion 4 can be formed by forming holes having adesired shape on the mask. The thickness of the close contact portion 4can be made non-uniform by disposing the lens A at an acute angle withrespect to the vapor deposition source 14 and rotating the lens A.

Etching may be performed to control the covering area and the thicknessof the close contact portion 4. Either dry etching or wet etching may beused. The shape of the close contact portion 4 can be adjusted into adesired shape by changing the ultrasonic wave frequency, temperature,and processing time.

Subsequently, as illustrated in FIG. 4D, in order to form a second resinlayer 2 in the lens B, a second resin 12 as a precursor of the secondresin layer 2 is formed between the lens B and a second substrate 6. Inthis case, the second resin 12 is a resin containing a curable resin.Subsequently, the distance between the lens B and the second substrate 6is adjusted so that the second resin layer 2 provides a desiredthickness.

Then, as illustrated in FIG. 4E, the second resin 12 is irradiated withultraviolet radiation from the ultraviolet light source 9 through thefirst substrate 5 or the second substrate 6. When the second resin 12 iscured, the second resin layer 2 is formed, and the diffractive opticalelement according to the present disclosure is obtained. In addition,the second substrate 6 may be removed after forming the second resinlayer 2.

<Method for Evaluating Diffractive Optical Element>

A method for evaluating the diffractive optical element according to thepresent disclosure will be illustrated below.

<Covering Area of Close Contact Portion to Grating Slopes>

The covering area of the close contact portion 4 to the area of thegrating slope in each annular of the diffraction grating was calculatedthrough the measurement of the transmitted wave front by using a Fizeauinterferometer.

As a result of the measurement of the transmitted wave front on thegrating slope having the close contact portion 4 of the diffractiveoptical element, the phase of the transmitted wave front differs betweena region where the close contact portion 4 is present and a region wherethe close contact portion 4 is absent. More specifically, when therefractive index of the close contact portion 4 is larger than therefractive index of the first resin layer 1 and the second resin layer2, the phase of the transmitted wave front in a region where the closecontact portion 4 is present has a phase lag behind the phase in aregion where the close contact portion 4 is absent. On the other hand,when the refractive index of the close contact portion 4 is smaller thanthe refractive index of the first resin layer 1 and the second resinlayer 2, the phase of the transmitted wave front in a region where theclose contact portion 4 is present has a phase lead to the phase in aregion where the close contact portion 4 is absent.

<Flare Rates>

The flare rate was evaluated before and after a high-temperaturedurability test (at 60° C. temperature and 70% humidity for 1200 hours).

The diffractive optical element was built in an imaging optical system(EF lens barrel manufactured by Canon, Inc.) modified for flare ratemeasurement, and flare light in the high refractive-index member wasmeasured. In the flare rate measurement, an image of a blackbody iscaptured by the imaging optical system incorporating the diffractiveoptical element to be measured, and then the imaging luminance isevaluated. A larger amount of flare light from the diffractive opticalelement produces a larger amount of leak light covering the blackbody,resulting in a higher imaging luminance of the blackbody. Forquantitative analysis of flare light, the luminance rate of leak lightby flare light to a perfect blackbody free from flare light wasanalyzed. More specifically, the flare rate was defined as the increaserate of the luminance by flare light covering the entire perfectblackbody on the assumption that the luminance of a white screen withoutblackbody is 100% and the luminance of the perfect blackbody is 0%. Theflare rate is desirably 0.15% and more desirably 0.10% or less. Thechange between the flare rates before and after the high-temperaturedurability test is desirably less than 0.05% and more preferably 0.02%or less.

<Optical Apparatus>

Next, an optical apparatus according to the present disclosure will bedescribed. The optical apparatus according to the present disclosureincludes a housing, and an optical system composed of a plurality oflenses disposed in the housing. At least one of the plurality of lensesis the above-described diffractive optical element.

FIG. 5 is a cross-sectional view illustrating an optical system of aninterchangeable lens barrel of a single-lens reflex camera as an exampleof a desirable exemplary embodiment of the optical apparatus accordingto the present disclosure. The optical system of a lens barrel 30includes lenses 21 to 29 and a diffractive optical element 20 disposedperpendicularly to the optical axis O in a housing 31. The side of thelens 21 is the incidence plane of external light, and the side of thelens 29 is the attachable/detachable mount side with a camera body.

By disposing the diffractive optical element 20 according to the presentdisclosure at a suitable position of the optical system, an opticalapparatus capable of preventing the generation of flare light even undera high-temperature environment can be achieved.

Exemplary Embodiments

The following specifically describes the diffractive optical elementaccording to exemplary embodiments of the present disclosure.

Now, a first exemplary embodiment will be described. A diffractiveoptical element illustrated in FIG. 6 was manufactured by using theproduction method described above with reference to FIGS. 4A to 4E.

As the first substrate 5, a glass meniscus lens (with a diameter of 60mm in planar view) was prepared. As the mold 10, a substrate stainlesssteel (product name: STAVAX from Bohler Uddeholm AG (BUAG)) as a basematerial plated with 200-μm NiP and processed into a saw bladecross-sectional shape by using a grinding machine was prepared.

An optically curable epoxy resin as the first resin 11 disposed on thefirst substrate 5 was press-transferred by using the mold 10. In thisstate, the first resin 11 was irradiated with ultraviolet radiationthrough the first substrate 5 so that the resin was cured. In thisultraviolet irradiation, an ultraviolet irradiation apparatus (productname: UV Light Source UL750 from HOYA CANDEO OPTRONICS) was used with adosage of 15 J/cm2 (with a 15-mW/cm2 illuminance for 1,000 seconds).After completion of the irradiation, when the mold 10 was released, thefirst resin layer 1 having a concentric diffraction grating shape wasformed on the first substrate 5. The obtained diffraction grating shapeis formed with a 10-μm height of the wall surfaces and a grating pitchfrom 0.1 to 3 mm. The grating pitch is the largest in the first annularand decreases with increasing distance toward the 80th annular as theoutermost edge. For the first resin layer 1, the refractive-index nd1was 1.58, the Abbe number ν1 was 32, and the linear expansioncoefficient at 0 to 40° C. was 6.2×10⁻⁵/° C.

Subsequently, to form the high refractive-index portion 3 on the wallsurfaces of the diffraction grating shape of the first resin layer 1 andto form the close contact portion 4 on the slopes, alumina (Al₂O₃) wasdeposited through a mask. Vapor deposition conditions for the highrefractive-index portion 3 includes an angle of 45 degrees with respectto the vapor deposition source 14, a rotational speed of 5 rpm, and afilm forming time of 20 minutes. For the high refractive-index portion3, the thickness was 200 nm, and the refractive index was 1.75.

Vapor deposition conditions for the close contact portion 4 include anangle of 90 degrees with respect to the vapor deposition source 14, anda film forming time of 15 minutes. The close contact portion 4 wasformed at positions from the center of the diffractive optical element100 to the distance of the radius R. For the close contact portion 4,the thickness was 100 nm ( 1/100 times the height of the wall surfaces),and the linear expansion coefficient at 0 to 40° C. was 0.8×10⁻⁵/° C. Inaddition, the covering area of the grating slope in each annularadjusted with the mask shape was 20 area portions in average.

As the second substrate 6, a concave glass lens was prepared. Anoptically curable acrylic resin as the second resin 12 between thesecond substrate 6 and the first resin layer 1 was adjusted so as toachieve a desired thickness. Then, the second resin 12 was irradiatedwith ultraviolet radiation through the second substrate 6 so that thesecond resin 12 was cured. Thus, the second resin layer 2 was formed,and the diffractive optical element according to the first exemplaryembodiment was obtained. For the second resin layer 2, therefractive-index nd2 was 1.61, the Abbe number ν2 was 41, and the linearexpansion coefficient at 0 to 40° C. was 8.4×10⁻⁵/° C.

Subsequently, the flare rates before and after the high-temperaturedurability test of the diffractive optical element according to thefirst exemplary embodiment were evaluated. As a result, the flare ratebefore the test was 0.03%, and the flare rate after the test was 0.04%.The change amount was 0.01% as a preferable value.

First Comparative Example

A diffractive optical element according to a first comparative examplewas manufactured by using a similar method to the first exemplaryembodiment except that alumina was deposited with the grating slopesmasked when the high refractive-index portion 3 and the close contactportion 4 are formed. Therefore, the diffractive optical elementaccording to the first comparative example had no close contact portion.

The flare rates before and after the high-temperature durability test ofthe diffractive optical element according to the first comparativeexample were evaluated. As a result, the flare rate before the test was0.03%, and the flare rate after the test was 0.31%. The change amountwas 0.28% as a larger value than the value according to the firstexemplary embodiment. After the high-temperature durability test, theinterface between the first resin layer 1 and the second resin layer 2was observed by using an electron microscope. As a result, theoccurrence of peeling was confirmed.

Second Comparative Example

A diffractive optical element according to a second comparative examplewas manufactured by using a similar method to the first exemplaryembodiment except that the rotational angle was changed when alumina(Al₂O₃) is deposited, and alumina (Al₂O₃) was uniformly deposited on thegrid wall surfaces and the grating slopes, without forming the closecontact portion 4. In other words, for the diffractive optical elementaccording to the second comparative example, the covering area of thegrating slopes was 100 area percent. In other words, according to thesecond comparative example, the close contact portion and the highrefractive-index portion were integrally and continuously formed.

For the high refractive-index portion 3, the thickness was 100 nm on thewall surfaces and the slopes, and the refractive index was 1.75.

The flare rates before and after the high-temperature durability test ofthe diffractive optical element according to the second comparativeexample were evaluated. As a result, the flare rate before the test was0.12%, and the flare rate after the test was 0.33%. The change amountwas 0.21% as a larger value than the value according to the firstexemplary embodiment. After the high-temperature durability test, theinterface between the first resin layer 1 and the high refractive-indexportion 3 and the interface between the second resin layer 2 and thehigh refractive-index portion 3 were observed by using an electronmicroscope. As a result, the occurrence of a crack near the slopes andthe occurrence of peeling at the interface between each resin layer andthe high refractive-index portion 3 were confirmed.

Next, a second exemplary embodiment will be described. A diffractiveoptical element according to a second exemplary embodiment wasmanufactured by using a similar method to the first exemplary embodimentexcept that the time for depositing alumina was prolonged from thataccording to the first exemplary embodiment and the mask shape waschanged when the high refractive-index portion 3 and the close contactportion 4 are formed and that the rotational angle was changed when thehigh refractive-index portion 3 is formed.

For the high refractive-index portion 3, the thickness was 300 nm, andthe refractive index was 1.75. For the close contact portion 4, thethickness was 200 nm, and the covering area of the grating slope in eachannular was 50 area percent on average.

The flare rates before and after the high-temperature durability test ofthe diffractive optical element according to the second exemplaryembodiment were evaluated. As a result, the flare rate before the testwas 0.08%, and the flare rate after the test was 0.10%. The changeamount was 0.02% as a preferable value.

Next, a third exemplary embodiment will be described. A diffractiveoptical element illustrated in FIG. 7 was manufactured by using theproduction method described above with reference to FIGS. 4A to 4E.

As the first substrate 5, a glass planar lens (with a diameter of 40 mmin planar view) was prepared. As the mold 10, a substrate stainlesssteel (product name: STAVAX from Bohler Uddeholm AG (BUAG)) as a basematerial plated with 200-μm NiP and processed into a saw bladecross-sectional shape by using a grinding machine was prepared.

An optically curable fluorine acrylic resin as the first resin 11disposed on the first substrate 5 was press-transferred by using themold 10. In this state, the first resin 11 was irradiated withultraviolet radiation through the first substrate 5 so as to cure theresin. In this ultraviolet irradiation, an ultraviolet irradiationapparatus (product name: UV Light Source UL750 from HOYA CANDEOOPTRONICS) was used with a dosage of 15 J/cm2 (with a 15-mW/cm2illuminance for 1,000 seconds). After completion of the irradiation,when the mold 10 was released, the first resin layer 1 having aconcentric diffraction grating shape was formed on the first substrate5. The obtained diffraction grating shape is formed with a 20-μm heightof the wall surfaces and a grating pitch from 0.1 to 2 mm. The gratingpitch is the largest in the first annular and decreases with increasingdistance toward the 35th annular as the outermost edge. For the firstresin layer 1, the refractive index was 1.49, the Abbe number ν1 was 33,and the linear expansion coefficient at 0 to 40° C. was 7.7×10⁻⁵/° C.

Subsequently, in order to form the high refractive-index portion 3 onthe wall surfaces of the diffraction grating shape of the first resinlayer 1, La-added alumina (La:Al₂O₃) was deposited via a mask. Vapordeposition conditions for the high refractive-index portion 3 includesan angle of 40 degrees with respect to the vapor deposition source 14, arotational speed of 8 rpm, and a film forming time of 7 minutes. For thehigh refractive-index portion 3, the thickness was 120 nm, and therefractive index was 1.71.

Subsequently, in order to form the close contact portion 4 on thegrating slopes at positions with a distance r of 4 to 40 mm from thecenter of the diffraction grating shape, silica (SiO₂) was deposited. Inthis case, a mask (not illustrated) was disposed between the wallsurfaces and the vapor deposition source 14 so that silica (SiO₂) doesnot adhere to the wall surfaces. Vapor deposition conditions for theclose contact portion 4 include an angle of 90 degrees with respect tothe vapor deposition source 14, and a film forming time of 10 minutes.For the close contact portion 4, the thickness was 20 nm ( 1/100 timesthe height of the wall surfaces), the refractive index was 1.45, and thelinear expansion coefficient at 0 to 40° C. was 0.8×10⁻⁵/° C. Thecovering area of the grating slope in each annular adjusted with themask shape was 70 area portions on average.

As the second substrate 6, a glass planar lens was prepared. Anoptically curable epoxy resin as the second resin 12 between the secondsubstrate 6 and the first resin layer 1 was adjusted so as to achieve adesired thickness. Then, the second resin 12 was irradiated withultraviolet radiation through the second substrate 6 to cure the secondresin 12. In this way, the second resin layer 2 was formed, and thediffractive optical element according to the third exemplary embodimentwas obtained. For the second resin layer 2, the refractive index was1.53, the Abbe number was 39, and the linear expansion coefficient at 0to 40° C. was 5.9×10⁻⁵/° C.

The flare rates before and after the high-temperature durability test ofthe diffractive optical element according to the first exemplaryembodiment were evaluated. As a result, the flare rate before the testwas 0.05%, and the flare rate after the test was 0.07%. Thus, the changeamount was 0.02% as a preferable value.

Next, a fourth exemplary embodiment will be described. The diffractiveoptical element illustrated in FIG. 1 was manufactured by using theproduction method described above with reference to FIGS. 4A to 4E.

As the first substrate 5, a glass meniscus lens (with a diameter of 100mm in planar view) was prepared. As the mold 10, a substrate stainlesssteel (product name: STAVAX from Bohler Uddeholm AG (BUAG)) as a basematerial plated with 200-μm NiP and processed into a saw bladecross-sectional shape by using a grinding machine was prepared.

An optically curable acrylic resin containing 16 volume percent ofdispersed ITO fine particles as the first resin 11 disposed on the firstsubstrate 5 was press-transferred by using the mold 10. In this state,the first resin 11 was irradiated with ultraviolet radiation through thefirst substrate 5 to cure the resin. In this ultraviolet irradiation, anultraviolet irradiation apparatus (product name: UV Light Source UL750from HOYA CANDEO OPTRONICS) was used with a dosage of 15 J/cm2 (with a15-mW/cm2 illuminance for 1,000 seconds). After completion of theirradiation, when the mold 10 was released, the first resin layer 1having a concentric diffraction grating shape was formed on the firstsubstrate 5. The obtained diffraction grating shape is formed with an8-μm height of the wall surfaces and a grating pitch from 0.1 to 5 mm.The grating pitch is the largest in the first annular and decreases withincreasing distance toward the 120th annular as the outermost edge. Forthe first resin layer 1, the refractive index was 1.62, the Abbe numberwas 19, and the linear expansion coefficient at 0 to 40° C. was3.2×10⁻⁵/° C.

Subsequently, in order to form the high refractive-index portion 3 onthe wall surfaces of the diffraction grating shape of the first resinlayer 1 and to form the close contact portion 4 on the slopes, Ti-addedalumina (Ti:Al₂O₃) was deposited via a mask. Vapor deposition conditionsfor the high refractive-index portion 3 includes an angle of 40 degreeswith respect to the vapor deposition source 14, a rotational speed of 10rpm, and a film forming time of 5 minutes. For the high refractive-indexportion 3, the thickness was 80 nm, and the refractive index was 1.81.

Vapor deposition conditions for the close contact portion 4 include anangle of 50 degrees with respect to the vapor deposition source 14, arotational speed of 6 rpm, and a film forming time of 7 minutes. For theclose contact portion 4, the thickness was 20 nm in the first annularand 80 nm in the 117th annular ( 1/400 or more and 1/100 or less timesthe height of the wall surfaces). The covering area of the grating slopein each annular adjusted with a mask shape was 5 area portions in thefirst annular, 99 area portions in the 117th annular, and 100 areaportions in the 118th to the 120th annulars. Since the 118th to the120th annulars are outside the optically effective area, these annularsdid not affect the diffractive efficiency. Ti:Al₂O₃ formed in the 118thto the 120th annulars is continuous to the high refractive-index portion3 of the wall surfaces, and therefore is not the close contact portion4.

As the second substrate 6, a concave glass lens was prepared. Anoptically curable acrylic resin containing 20 volume % of dispersedzirconia fine particles as the second resin 12 between the secondsubstrate 6 and the first resin layer 1 was adjusted so as to achieve adesired thickness. Then, when the second resin 12 was irradiated withultraviolet radiation via the second substrate 6 to cure the secondresin 12, and thus the second resin layer 2 was formed. Then, the secondsubstrate 6 is removed. Thus, the diffractive optical element accordingto the fourth exemplary embodiment was obtained. For the second resinlayer 2, the refractive-index nd2 was 1.66, the Abbe number ν2 was 45,and the linear expansion coefficient at 0 to 40° C. was 2.9×10⁻⁵/° C.

Subsequently, the flare rates before and after the high-temperaturedurability test of the diffractive optical element according to thefourth exemplary embodiment were evaluated. As a result, the flare ratebefore the test was 0.09%, and the flare rate after the test was 0.11%.Thus, the change amount was 0.02% as a preferable value.

The above-described results are summarized in Table 1.

TABLE 1 First First Second Second Third Fourth exemplary comparativecomparative exemplary exemplary exemplary embodiment example exampleembodiment embodiment embodiment Substrate Diameter 60 60 60 60 40 100(mm) First Material Epoxy Epoxy Epoxy Epoxy Acrylic Acrylic resin resinresin resin resin resin resin layer containing ITO Height 10 10 10 10 208 of grid wall surfaces (μm) Grating 0.1-3 0.1-3 0.1-3 0.1-3 0.1-20.1-5   pitch (mm) Refractive 1.58 1.58 1.58 1.58 1.49 1.62 index nd1Abbe 32 32 32 32 33 19 number v1 Linear 6.2 × 10⁻⁵ 6.2 × 10⁻⁵ 6.2 × 10⁻⁵6.2 × 10⁻⁵ 7.7 × 10⁻⁵ 3.2 × 10⁻⁵ expansion coefficient Second MaterialAcrylic Acrylic Acrylic Acrylic Epoxy Acrylic resin resin resin resinresin resin resin layer containing zirconia Refractive 1.61 1.61 1.611.61 1.53 1.66 index nd2 Abbe 41 41 41 41 39 45 number v2 Linear 8.4 ×10⁻⁵ 8.4 × 10⁻⁵ 8.4 × 10⁻⁵ 8.4 × 10⁻⁵ 5.9 × 10⁻⁵ 2.9 × 10⁻⁵ expansioncoefficient High Material Al₂O₃ Al₂O₃ Al₂O₃ Al₂O₃ La:Al₂O₃ Ti:Al₂O₃refractive- Thickness 200 200 200 300 120 80 index (nm) portionRefractive 1.75 1.75 1.75 1.75 1.71 1.81 index Close Material Al₂O₃ NoneAl₂O₃ Al₂O₃ SiO₂ Ti:Al₂O₃ contact Thickness 100 100 200 20 20-80 portion(nm) Thickness 1/100 1/100 1/50 1/100 1/400- 1/100 (to wall surface)Covering 20 100 50 70  5-99 area (area portion) Range 0-R 0-R 0-R 0.1R-R0-0.98R Linear 0.8 × 10⁻⁵ 0.8 × 10⁻⁵ 0.8 × 10⁻⁵ 0.8 × 10⁻⁵ 1.5 × 10⁻⁵expansion coefficient Diffractive Flare 0.03 0.03 0.12 0.08 0.05 0.09optical rate element before test (%) Flare 0.04 0.31 0.33 0.1 0.07 0.11rate after test (%) Flare 0.01 0.28 0.21 0.02 0.02 0.02 change rate (%)

Based on the above-described results, it turned out that, before andafter the high-temperature durability test, the first to the fourthexemplary embodiments in which the close contact portion having athickness smaller than the height of the wall surfaces is disposed onthe slopes can achieve flare rates lower than those according to thefirst and the second comparative examples.

According to the present disclosure, it is possible to offer adiffractive optical element with reduced generation of flare light,capable of preventing the occurrence of peeling in the interface betweenthe first and the second resin layers even after being neglected in ahigh-temperature environment for a prolonged period of time.

While the present disclosure has been described with reference toexemplary embodiments, it is to be understood that the invention is notlimited to the disclosed exemplary embodiments. The scope of thefollowing claims is to be accorded the broadest interpretation so as toencompass all such modifications and equivalent structures andfunctions.

This application claims the benefit of Japanese Patent Application No.2018-150555, filed Aug. 9, 2018, which is hereby incorporated byreference herein in its entirety.

What is claimed is:
 1. A diffractive optical element comprising: asubstrate; a first resin layer formed on the substrate and having adiffraction grating shape including a plurality of wall surfaces and aplurality of slopes; a second resin layer formed on the first resinlayer; a first portion formed on the plurality of wall surfaces of thefirst resin layer and having a higher refractive index than the firstand the second resin layers; and a second portion discontinuous with thefirst portion and the plurality of wall surfaces, wherein the secondportion is formed on the plurality of slopes of the first resin layer,wherein a thickness of the second portion in a direction normal to asurface of the plurality of slopes is smaller than a height of theplurality of wall surfaces, wherein a length of the first portionparallel to the plurality of wall surfaces is the same as or larger thanthe height of the plurality of wall surfaces, and wherein the thicknessof the first portion in a direction normal to the plurality of wallsurfaces is greater than the thickness of the second portion.
 2. Thediffractive optical element according to claim 1, wherein the thicknessof the second portion is 1/400 or more and 1/50 or less times the heightof the plurality of wall surfaces.
 3. The diffractive optical elementaccording to claim 1, wherein the thickness of the second portion is 10nm or more and 200 nm or less.
 4. The diffractive optical elementaccording to claim 1, further comprising a center and an outer edge,wherein the thickness of the second portion increases with increasingdistance from the center toward the outer edge.
 5. The diffractiveoptical element according to claim 1, wherein a covering area of thesecond portion to the plurality of slopes is 5 or more and 99 or lessarea portions with respect to 100 area portions on the plurality ofslopes.
 6. The diffractive optical element according to claim 1, furthercomprising a center and an outer edge, wherein a covering area of thesecond portion to the plurality of slopes increases with increasingdistance from the center toward the outer edge.
 7. The diffractiveoptical element according to claim 1, further comprising a center and anouter edge, wherein, in a planar view of the diffractive optical elementviewed from the direction in which the first and the second resin layersare stacked, the second portion is formed on the plurality of slopes ina region satisfying the formula (1):0.1R≤|r|≤R  (1) where R denotes a radius of the diffractive opticalelement, and r denotes a distance from the center toward the outer edge.8. The diffractive optical element according to claim 1, wherein thesecond portion is made of an inorganic material.
 9. The diffractiveoptical element according to claim 1, wherein the first portion is madeof an inorganic material.
 10. The diffractive optical element accordingto claim 1, wherein the second portion is made of a same material as thefirst portion.
 11. The diffractive optical element according to claim 1,wherein a linear expansion coefficient of the second portion at 0 to 40°C. is 1/10 or more times the linear expansion coefficient of the firstand the second resin layers at 0 to 40° C.
 12. The diffractive opticalelement according to claim 1, wherein nd1<nd2 and v1<v2 are satisfied,where nd1 denotes the refractive index of the first resin layer, v1denotes the Abbe number of the first resin layer, nd2 denotes therefractive index of the second resin layer, and v2 denotes the Abbenumber of the second resin layer.
 13. The diffractive optical elementaccording to claim 1, wherein a second substrate is stacked on thesecond resin layer.
 14. An optical apparatus comprising: a housing; andan optical system having lenses arranged in the housing, wherein atleast one of the lenses is the diffractive optical element according toclaim
 1. 15. The diffractive optical element according to claim 1,wherein the thickness of the second portion is 10 nm or more and 200 nmor less, and wherein the thickness of the first portion is 1.0 μm orless.